18027-46-8Relevant articles and documents
Reduction of Carbonyl Compounds with Hydrosilanes on Solid Acid and Solid Bases
Onaka, Makoto,Higuchi, Katsumi,Nanami, Hiroyuki,Izumi, Yusuke
, p. 2638 - 2645 (1993)
Hydrosilylations of carbonyl compounds were performed on the surfaces of solid acids and bases.Strongly acidic clays efficiently catalyzed the reduction of aldehydes and ketones with trialkylsilanes (e.g.Et3SiH) to afford symmetrical ethers or hydrocarbons, depending upon the characters of substituents around carbonyl groups.Reduction-resistant ketone like 4,4'-dimethoxybenzophenone was found to be reduced with Et3SiH under the catalytic influence of the highly acidic clay.In contrast, trialkoxysilanes (e.g. (EtO)3SiH) became labile in contact with solid base like hydroxyapatite, reducing a variety of carbonyl compounds to yield alkoxy(triethoxy)silane in good yields.It was revealed that besides fluoride salts, solid bases bearing mild basicity and relatively large surface areas can activate the trialkoxysilane enough for reduction of carbonyl functions.
RHODIUM(II) COMPLEXES AS HYDROSILYLATION AND HYDROGENATION CATALYSTS
Howe, J.P.,Lung, K.,Nile, Terence A.
, p. 401 - 406 (1981)
Two phosphine-rhodium(II) complexes, bis(tris-o-tolylphosphine)dichlororhodium(II) and bis(tricyclohexylphosphine)dichlororhodium(II), have been found to be active catalysts for the hydrosilylation of a variety of organic substrates, and, in conjunction with triethylaluminum, to be hydrogenation catalysts.
Preparation of hydrido [CNC]-pincer cobalt complexes via selective C-H/C-F bond activation and their catalytic performances
Yang, Fei,Wang, Yangyang,Lu, Faguan,Xie, Shangqing,Qi, Xinghao,Sun, Hongjian,Li, Xiaoyan,Fuhr, Olaf,Fenske, Dieter
, p. 15578 - 15586 (2018/10/04)
Polyfluorinated aryl imines 2,4,5-R1,R2,R3-C6H2-HC═N-1-C10H7 (R1 = F, R2 = F, R3 = H (1); R1 = F, R2 = H, R3 = F (2) and R1 = F, R2 = F, R3 = F (3)) and F5C6-HC═N-1-C10H7 (7) reacted with CoMe(PMe3)4 to give rise to hydrido [CNC]-pincer cobalt(iii) complexes (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(H)(PMe3)2 (R1 = F, R2 = F, R3 = H (4); R1 = F, R2 = H, R3 = F (5); R1 = F, R2 = F, R3 = F (6)) and (F4C6-HC═N-1-C10H6)Co(H)(PMe3)2 (8) via selective C-F/C-H bond activation. Penta-coordinate dicarbonyl cobalt(i) complexes (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H7)Co(CO)2(PMe3) (R1 = F, R2 = H, R3 = F (9); R1 = F, R2 = F, R3 = F (10)) were obtained from reactions of hexa-coordinate cobalt(iii) complexes 5 and 6 with carbon monoxide through reductive elimination. Cobalt(iii) halides (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(i)(PMe3)2 (R1 = F, R2 = F, R3 = H (11); R1 = F, R2 = H, R3 = F (12); R1 = F, R2 = F, R3 = F (13)) and (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(Br)(PMe3)2 (R1 = F, R2 = F, R3 = H (14); R1 = F, R2 = H, R3 = F (15); R1 = F, R2 = F, R3 = F (16)) were prepared by the interaction between hydrido cobalt(iii) complexes 4-6 and MeI or EtBr. The molecular configurations of complexes 4, 8, and 11 were determined by single crystal X-ray diffraction. We then confirmed that the four hydrido cobalt(iii) complexes 4-6 and 8 could be used as catalysts for reduction of aldehydes and ketones. Complex 8 is the best catalyst among the four complexes and can selectively catalyze the carbonyl groups of α,β-unsaturated aldehydes and ketones.
Synthesis of [POCOP]-pincer iron and cobalt complexes via Csp3-H activation and catalytic application of iron hydride in hydrosilylation reactions
Huang, Shaofeng,Zhao, Hua,Li, Xiaoyan,Wang, Lin,Sun, Hongjian
, p. 15660 - 15667 (2015/03/05)
Csp3-H bond activation in diphosphinito pincer ligand (Ph2PO(o-C6H2-(4,6-tBu2)))2CH2 (1) (POCH2OP) was achieved by Fe(PMe3)4 and CoMe(PMe3)4 to afford complexes (POCHOP)Fe(H) (PMe3)2 (2) and (POCHOP)Co(PMe3)2 (4) under mild conditions. Hydrido iron complex 2 reacted with iodomethane via the elimination of methane to deliver complex (POCHOP)FeI(PMe3) (3). The ligand replacement in Ni(PMe3)4 by 1 gave rise to nickel(0) complex (POCH2OP)Ni(PMe3)2 (5) without Csp3-H bond activation of the pincer ligand (1). It was confirmed that the hydrosilylation of aldehydes and ketones could be effectively catalyzed by hydrido iron complex 2. Complexes 2-5 were characterized by spectroscopic methods and X-ray single crystal diffraction analysis. This journal is
